NANOHUNTER

-Benchtop TXRF-

Rigaku

Contents

1. Position of NANOHUNTER
2. Performance of NANOHUNTER

3. Application
4. Specification

2006.8.4

XRF
X-ray Fluorescent Spectrometory

Irradiation of
X-rays

Qualitative and Quantitative

Element Analysis
Feature
Non-distractive
Fluorescent X-rays
Fast
Easy preparation

Material

Field
Steel
Ceramics
Plastics
Semiconductor
Others

Important Surface Quality Control

Quality control
Hazard material
Impurities

Direct influence to human

Glass
Metal
Plastic
Ceramics Degradation of performance
Semiconductor
Peel of film
Crack in film
Film
Failure in operation
Evaporation or liquid coating

TXRF
Sensitive on Surface
Total reflection occurs with the
glancing angle irradiation.

Incident X-rays

Incident X-rays excite atoms only

in the region of several nm near
the surface
Total Reflection

5 nm
Material

Application
Owing to the sophisticated optics
Applicable for both solid and liquid
Surface of solid :
Contamination

Diffusion
NANOHUNTER

1. High sensitivity
2. Small amount of sample
3. Angle dependence
4. High Stability

Liquid :
Quantitative analysis

Feature of TXRF
Contamination on a stainless steel
sample

High Background
escape

F> F C
Glancing Angle higher than critical angle

High Sensitivity
Low background
High P/B ratio
F< F C
Glancing Angle lower than critical angle

Depth distribution information

Angle dependence data shows Pb
exist only on the surface of the
steel.

Steel samples

1400

Intensity
X-ray X

1200
1000
800
600

Intensity
X-rayX

Fe-Ka
Pb-La

400
200
0
0

Small amount of
Pb was found.

Mo-Ka

Fe

0.05
0.1

Angle (deg)

10
9
8
7
6
5
4
3
2
1
0

0.15

Mo-Ka
Fe-Ka
Pb-La

Pb
0

0.05

0.1

Angle
(deg)

0.15

Impurities in deposited films

Impurity metals included in a film can be detected with NANOHUNTER.
The example is a Ag film deposited in a vacuum. W impurity was found in the film
with NANOHUNTER.
W is considered to be deposited with Ag in a vacuum chamber.

Glass Substrate

Ag
W wire

Detection limit for impurity atoms on a surface

- atoms/cm2 LLD (Fe) = 3x1011atoms/cm2
LLD (Ni) = 1.5x1012atoms/cm2
LLD (Br) = 7x1011atoms/cm2
Reference;
Density of Si atoms on Si(100) surface
6x1014atoms/cm2

NANOHUNTER

Cu-Ka
Ar-Ka

Sn-La
K-Ka

Ca-Ka

Fe-Ka

Si-Ka

Angle dependence of Si-Ka and Ca-Ka intensity

shows typical curve by bulk type distribution.
Intensities of Fe-Ka and Sn-La are
constant in a range over the critical angle.
This means a dense area of Fe and Sn
exists only near the surface.

Energy
X

Sn and Fe

Si, Ca

Soda lime glass

X-ray Intensity

X
X-ray Intensity

Soda lime glass

Critical angle

Glancing Angle (deg)

Sn

Penetration of incident X-rays

-Theoretical calculationIncident X-ray distribution of Cu-Ka in a Soda lime Glass
2

0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.26
0.28
0.30

1.8

Relative X-ray Intensity

1.6
1.4
1.2

0.24; over the critical angle

0.28

0.8

0.26

0.6

0.22; below the critical angle

0.4

0.18 0.20

0.2
0
0

10

20

30
Depth (nm)

40

50

Soda lime glass

Over the critical angle

Sn-La
Sn-La

Sn-La
Intensity
X-ray

f=0.35deg

5
4
3
2
1
0
A

100

X-ray Intensity

Glancing angle;f=0.15deg
Under the critical angle
Sn-La

80
60
40
20
0

Sample

180
160
140
120
100
80
60
40
20
0

X-ray Intensity

Fe-Ka

Fe-Ka
Intensity
X-ray

Sample

Fe-Ka

9
8
7
6
5
4
3
2
1
0
B

Sample

Fe-Ka

Sample

Thin Film
CoFe(10%Fe) 10nm
Si
Angle Dependence
Linear Scale

Log Scale
Co-Ka

Co-Ka
Fe-Ka

Si-Ka
Cu-Ka
Ar-Ka

Si-Ka
Fe-Ka

Cu-Ka

Angle (deg)

Angle (deg)

f=0.15deg

Double layered thin film

Au 5nm
Cu 5nm
Glass

CuKa

f=0.25deg

MoKa

CaKa
AuLa

FeKa
SiKa

f=0.50deg

Evaluation of distribution on surface

HANOHUNTER can distinguish the distribution type
Film Type
Ni

Ni

Ni

Intermediate Type
Ni

Ni

Ni

Particle Type
Ni

Ni
Ni

1.2
1.0

Relative intensity

Film

0.8

Intermediate

0.6

Particle

0.4
0.2
0.0
0.04

0.08

0.12

0.16

0.2

Glencing angle (deg)

0.24

0.28

Particle Type

Particle Type
Black maker
CaKa
CrKa

CuKa

SiKa
FeKa

Angle (deg)

Angle dependence

Liquid
Drop and Dry
Pipette

*Simple and Easy

*Small amount : 10mL-50mL

Drop to a substrate

Dry

Flow to prepare liquid sample

preparation

Sample

Drop
and
Dry

measurement

Qualitative
Analysis

Select
Internal STD
element

Drop
and
Dry

measurement

A
B

Add Internal
STD element
Relative
sensitivity

Quantitative
Analysis

Preparation of liquid
Water solution
Organic Solvent
(low boiling temperature)
Water including
organic materials

Organic Solvent
(high boiling temperature)

Drop
&
Dry
on a
Substrate
Acing
(dry or wet)

Qualitative
analysis
Quantitative
analysis

Calibration curve for ppb level S and Fe

S in water

Fe in water

corrected with internal standard of Sc

Mn 10ppb peak

Measureting time : 500sec

Liquid amount : 50 ml
Excitation: Cu-Ka

Lower Limit of Detection for

liquid solution

NANOHUNTER 500sec

LLD (ppb)

100

10
S
Sn

1
Cr

Pb

Cd

Zn
As

500
sec.
Sample
amount ;50L
30ml , Meas. Time;
500 sec

0.1
10

20

30

40

50 60
Atomic
Number

70

80

90

Comparison with ICP(1)

Mineral water vanadium included
Cu-Ka excitation

Mo-Ka excitation

* Internal standard : Co 0.5 ppm

unitppm
elem
ent

NANOHUNTER

ICP-AES

Label

31.92

35.4511

Cl

54.78

82.015

3.68

4.6495

2.5

Ca

16.22

13.13

20

0.119

0.1265

0.14

Cu

0.044

0.0561

Zn

0.016

0.009

Br

0.117

0.2608

Sr

0.064

0.0577

Comparison with ICP(2)

ppm

River water

*internal standard :Co 1.0 ppm

eleme
nt

NANOHUNTER

ICP-AES (A)

IICP-AES
(B)
IC (C)

8.80

7.6789

7.9

Cl

52.15

49.4077

33(IC)

13.35

8.4280

6.7

Ca

28.93

20.6721

22

Fe

0.009

0.0072

0.085

Br

0.137

0.0536

<0.1(IC)

Sr

0.081

0.071

Fuel
side

Load
H2,
(CO)

O2

Negativ
e
electrod
e

Drain

Air
side

Analysis of fuel cell waste fluid

Positive
electrod
e

Electrolyt Cathode
Anode
e Carbon loaded
Carbon loaded
with Pt catalyst

with Pt catalyst

Drain

S & Fe

Analysis of fuel cell waste fluid

Waste fluid
port

F- (ppb)

SO42- (ppb)

SO42- (ppb)

Fe ion (ppb)

Low
humidity
mode

Anode

63

(14.3)

1.7

Cathode

31

(10.1)

1.1

Anode

52

473

467.7

4.3

Cathode

36

1152

1045.1

2.2

High
humidity
mode

Ion chromatography

X*
NANOHUNTER

Humidity
condition

Cool type by B

Liquid
Lotion

Wet type by A

Wet type by B

Gunshot residue

Gunshot residue taken with a

adhesive tape
Ratio of Pb, Fe, Hg, Sb et on
the tape can identify
the type of the gun

One piece of Human Hair

Mo-Ka Excitation

Cu-Ka Excitation

Applicable to Many kind of Samples

Standard

76 x 26 mm

Silicon Wafer

16 peaces
Thickness : from 0.5mm to 5 mm

Hard disk

Tile

Rigaku Total Reflection X-ray Spectrometers

-World Leader in TXRFNANOHUNTER

TXRF300

Solid ; glass, steel, plastics, ceramics

Liquid ; water, oil, colloid solution

Solid ; Si wafer, FPD Substrate

Liquid ; Residue of HF

50W X-ray Tube

9kW X-ray Tube

Water cooled

Vacuum

Liq. N2

Air cooled

Air

LLD (Fe) = 3x1011atoms/cm2

LLD (Ni) = 1.5x1012atoms/cm2
LLD (Br) = 7x1011atoms/cm2

LLD (Fe) = 9x108atoms/cm2

LLD (Ni) = 9x108atoms/cm2
LLD (Br) = 1x1010atoms/cm2

History of TXRF
+VPD
Conventional
XRF

For Semiconductors
only

Invented by Dr. Yoneda

and Dr. Horiuchi in 1971
Around
1985
Bigining of
TXRF

General

Technology

Material
Chemical

NANOHUNTER

General

Environmental
Small but high quality

Full automatic alignment system

NANOHUNTER
Detector

X-ray Tube

Monochromator
PC

Cu

Mo
Shutter

Sample

All axes are

full-automatically
controlled

New
Technology

Plug in only
Output

Input
AC100-240V

Exhaust

Water

Liq.N2

Gas

Waste

NANOHUNTER